Ketenylidentriphenylphosphoran-Komplexe / Ketenylidenetriphenylphosphorane Complexes

Abstract

<jats:title>Abstract</jats:title><jats:p>Ketenylidenetriphenylphosphorane complexes of the type L<jats:sub>n</jats:sub>MC(CO)PPh<jats:sub>3</jats:sub> L<jats:sub>n</jats:sub>M = CpMn(CO)<jats:sub>2</jats:sub> (2a), CpRe(CO)<jats:sub>2</jats:sub> (2b) and Fe(CO)<jats:sub>4</jats:sub> (3) are obtained by CO substitution reactions. The synthesis of 3 at 80 °C is accompanied by the formation of a Fe<jats:sub>2</jats:sub>(CO)<jats:sub>6</jats:sub> compound with a bridging α-metallated formyl(triphenylphosphane)carbido ligand. From ethylation of 3 arises an Fe<jats:sub>2</jats:sub>(CO)<jats:sub>6</jats:sub> ferrol-type complex 5.</jats:p>

Organometallic Chemistry of Ph3PCCO. Synthesis, Characterization, X-ray Structure Determination, and Density Functional Study of the First Stable Bis-η1-ketenyl Complex,trans-[PtCl2{η1-C(PPh3)CO}2]

“…C 3 O 2 also gives monoinsertion reactions into a Pt−oxygen bond and some metal−hydride bonds as well, yielding compounds where an η 1 -ketenyl fragment and a carbonylic functionality are present. Furthermore, it was observed that the oxocumulenic ylide Ph 3 PCCO, 1 , is able to displace a weakly bonded ligand (CO or acetonitrile) from some low-valence complexes of early and medium transition metals, giving, by coordination through the ylidic carbon, η 1 -ketenyl derivatives in which PPh 3 is the second ketene substituent . Incidentally, η 1 -ketenyl derivatives can be considered as a peculiar kind of ketenes, bearing two different substituents, an organic moiety and a metal center.…”

Reaction of Ketenylidenetriphenylphosphorane (Ph3PCCO) with Platinum(II) and Palladium(II) Complexes. Synthesis, Characterization, and Molecular Structure of [Pt(η3-C3H5){η1-C(PPh3)(CO)}(PPh3)]BF4

“…Peculiar η 1 -ketenyl derivatives, in which the second substituent of the ketene moiety is SiMe 3 , have been obtained by reaction of Me 3 PCHSiMe 3 with [FeCp(CO) 2 ]I followed by rearrangements and, more recently, by Wolff rearrangement of a Rh diazolkane complex substitutes CO or MeCN from some early or medium transition metal complexes giving η 1 -ketenyl derivatives, e 1 …”

Group 9 and 10 Metal Complexes of an Ylide-Substituted Phosphine: Coordination versus Cyclometalation and Oxidative Addition

“…To the best of our knowledge such a secondary arene interaction with an aryl phosphonium moiety has never been observed for nickel. 11 This interaction in [ 1 ·Ni(CO) 2 ] becomes evident from short Ni–C interactions to the ipso and ortho carbon atoms, which range between 2.243(2) and 2.404(2) Å. It is interesting to note that the two molecules in the asymmetric unit show quite different Ni–C distances, which suggests that the interaction is only weak and sensitive to packing effects.…”